US5084429A - Catalysts for polymerization of olefins - Google Patents

Catalysts for polymerization of olefins Download PDF

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US5084429A
US5084429A US07/563,613 US56361390A US5084429A US 5084429 A US5084429 A US 5084429A US 56361390 A US56361390 A US 56361390A US 5084429 A US5084429 A US 5084429A
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solid product
titanium
halide
component
vanadium
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Masami Tachibana
Toshihiro Uwai
Tetsuya Matsukawa
Teruaki Hayashida
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JNC Corp
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Chisso Corp
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Priority claimed from JP22094889A external-priority patent/JP2811325B2/ja
Priority claimed from JP26867789A external-priority patent/JP2811333B2/ja
Priority claimed from JP26867889A external-priority patent/JP2811334B2/ja
Priority claimed from JP1574890A external-priority patent/JP2838224B2/ja
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Assigned to CHISSO CORPORATION reassignment CHISSO CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: HAYASHIDA, TERUAKI, MATSUKAWA, TETSUYA, TACHIBANA, MASAMI, UWAI, TOSHIHIRO
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

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  • This invention relates to catalysts useful for polymerization of alpha-olefins and more particularly, to a titanium halide catalytic component supported on magnesium compounds and a catalyst system comprising such a supported catalytic component.
  • Catalysts on magnesium-containing carriers which have high catalytic activity and good stereospecificity have been developed and are known to be suitable for vapor phase polymerization of alpha-olefins because of their advantages that the treatment of the catalyst residue in produced polymer is easy and that removal of App components is not necessary.
  • the catalysts for the vapor phase polymerization of alpha-olefins are further required to have a good shape of particles with a narrow distribution of particle size, a good shatter resistance and a high bulk density.
  • One of techniques for obtaining a controlled shape of catalyst particles is described in Japanese Laid-open Patent Application No. 63-54,405 wherein magnesium compounds are dissolved in an alcohol in the presence of carbon dioxide and treated with a mixture of a titanium halide and an organosilane to cause precipitation, to which a cyclic ether compound is added for re-dissolution and recrystallization, thereby obtaining a carrier with a good shape, and the carrier is activated to provide a catalyst.
  • catalyst particles prepared from a solution by a precipitation method involve the inevitable drawback that although particles of the carrier are uniform with a sharp distribution of particle size, part of the particles is broken in a subsequent activation step. In addition, particles of a larger size are more liable to break.
  • Japanese Laid-open Patent Application No. 63-54,405 there is the problem that when the particle size is as large as 30 ⁇ , the particles are broken in large amounts during the activation treatment such as with titanium halides, so that fine powder increases in amount.
  • a method for producing a large-sized supported catalyst wherein a specific type of silane compound, e.g. an alkylsilane alkoxide, is used as a shape control agent at the time of precipitation from solution and wherein when a cyclic ether is added for recrystallization, an alcohol is added by which in the preparation of a catalytic component and, particularly, a particulate catalyst with a large size, the particles suffer little or only a slight degree of degradation during the treatment with titanium halides.
  • a specific type of silane compound e.g. an alkylsilane alkoxide
  • a process for preparing a large-sized catalyst of the supported type wherein a specific type of silane compound, i.e. an alkylsilane alkoxide, is used as a shape-controlling agent at the time of precipitation from solution and an alcohol is added to a recrystallization system to which a cyclic ether compound has been added, by which a catalytic ingredient is prepared and particularly, a large-sized catalyst is prepared without any breakage thereof during treatment with titanium halides or with the particles being broken only in small amounts, if any.
  • a specific type of silane compound i.e. an alkylsilane alkoxide
  • the present invention of the first aspect is based on the method disclosed in Japanese Laid-open Patent Application No. 63-54,405 wherein a solid precipitate is formed from an alcohol solution of a magnesium compound by treatment with a titanium halide and is re-precipitated from a solution containing a cyclic ether.
  • the improvement resides in that the re-precipitation is effected in the presence of a boron compound, so that the resultant precipitate of the magnesium compound is unlikely to break and can be prevented from breaking in a subsequent treatment with titanium halide with a sharp size distribution.
  • TiX p OR 6 ) 4-p
  • X represents Cl or Br
  • R 6 represents an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms and p is an integer of from 1 to 4, and/or a vanadyl halide of the general formula, VO xq (OR 7 ) 3-q , and/or a vanadium halide of the general formula, VX r (OR 8 ) 4-r , wherein each X represents Cl or Br, R 7 and R 8 are independently an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, q is an integer of from 1 to 3 and r is an integer of from 1 to 4, and/or a silane halide of the
  • component (D) consisting of a titanium halide of the general formula, TiX p (OR 6 ) 4-p , wherein X represents Cl or Br, R 6 represents an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms and p is an integer of from 1 to 4, and/or a vanadyl halide of the general formula, VO xq (OR 7 ) 3-q , and/or a vanadium halide of the general formula, VX r (OR 8 ) 4-r , wherein each X represents Cl or Br, R 7 and R 8 are independently an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, q is an integer of from 1 to 3 and r is an integer of from 1 to 4, thereby obtaining
  • the molar ratio of titanium and magnesium is in the range of from 0.5 to 10:1 and the molar ratio of the electron donor and titanium is in the range of from 0.2 to 20:1.
  • the solid product (IV) obtained above may be further reacted with (g) the component (B) consisting of a titanium halide of the general formula, TiX p (OR 6 ) 4-p , wherein X represents Cl or Br, R 6 represents an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms and p is an integer of from 1 to 4, a vanadyl halide of the general formula, VO xq (OR 7 ) 3-q , and a vanadium halide of the general formula, VX r (OR 8 ) 4-r , wherein each X represents Cl or Br, R 7 and R 8 are independently an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, q is an integer of from 1 to 3 and r is an integer of from 1 to 4.
  • TiX p OR 6
  • the catalytic component defined above should preferably be used in combination with an organometallic compound with or without further combination with an electron donor as a third ingredient, thereby producing a catalyst system which is particularly useful for use in polymerization of alpha-olefins.
  • a catalytic component for use in polymerization of olefins which comprises a carrier mainly composed of a magnesium compound precipitated from a solution and a catalytic component supported on the carrier and selected from titanium halides, vanadyl halides and vanadium halides, the catalyst being obtained by a procedure which comprises:
  • TiX p OR 6 ) 4-p
  • X represents Cl or Br
  • R 6 represents an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms and p is an integer of from 1 to 4, and/or a vanadyl halide of the general formula, VOX q (OR 7 ) 3-q , and/or a vanadium halide of the general formula, VX r (OR 8 ) 4-r , wherein each X represents Cl or Br, R 7 and R 8 are independently an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, q is an integer of from 1 to 3 and r is an integer of from 1 to 4, and/or a silane halide of the
  • component (D) consisting of a titanium halide of the general formula, TiX p (OR 6 ) 4-p , wherein X represents Cl or Br, R 6 represents an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms and p is an integer of from 1 to 4, and/or a vanadyl halide of the general formula, VOX q (OR 7 ) 3-q , and/or a vanadium halide of the general formula, VX r (OR 8 ) 4-r , wherein each X represents Cl or Br, R 7 and R 8 are independently an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, q is an integer of from 1 to 3 and r is an integer of from 1 to 4 to obtain solid product
  • the alcohol used in the step (C) should preferably be a linear alcohol having from 2 to 10 carbon atoms.
  • the catalytic component defined above should preferably be used in combination with an organometallic compound with or without further combination with an electron donor as a third ingredient.
  • a catalytic component for use in polymerization of olefins which comprises a carrier mainly composed of a magnesium compound precipitated from a solution and a catalytic component supported on the carrier and selected from titanium halides, vanadyl halides and vanadium halides, the catalytic component being obtained by a procedure which comprises:
  • TiX p OR 6 ) 4-p
  • X represents Cl or Br
  • R 6 represents an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms and p is an integer of from 1 to 4, and/or a vanadyl halide of the general formula, VOX q (OR 7 ) 3-q , and/or a vanadium halide of the general formula, VX r (OR 8 ) 4-r , wherein each X represents Cl or Br, R 7 and R 8 are independently an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, q is an integer of from 1 to 3 and r is an integer of from 1 to 4, and/or a silane halide of the
  • component (D) consisting of a titanium halide of the general formula, TiX p (OR 6 ) 4-p , wherein X represents Cl or Br, R 6 represents an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms and p is an integer of from 1 to 4, and/or a vanadyl halide of the general formula, VOX q (OR 7 ) 3-q , and/or a vanadium halide of the general formula, VX r (OR 8 ) 4-r , wherein each X represents Cl or Br, R 7 and R 8 are independently an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, q is an integer of from 1 to 3 and r is an integer of from 1 to 4 to obtain solid product
  • the alcohol used in the step (C) should preferably be a linear alkyl alcohol having from 2 to 10 carbon atoms.
  • the catalytic component defined above should preferably be used in combination with an organometallic compound with or without further combination with an electron donor as a third ingredient.
  • a catalytic ingredient for polymerization of olefins which comprises a carrier made primarily of a Mg compound precipitated from its solution and a titanium halide, vanadyl halide or vanadium halide supported on the carrier and which consists essentially of a solid product (IV) obtained by a process which comprises:
  • the alcohol used in the step (C) should preferably be a linear alcohol having from 2 to 10 carbon atoms.
  • the catalytic ingredient defined above may be used in combination with an organometallic compound with or without further combination with an electron donative compound used as a third ingredient whereby such combinations are particularly suitable for use as a catalyst for polymerization of alpha-olefins.
  • the four figures are flow charts illustrating processes for preparing catalytic ingredients according to the invention.
  • step A is described.
  • step A (a) a magnesium compound of the general formula, Mg(OR 1 ) n (OR 2 ) 2-n or MgR 3 m (OR 4 ) 2-m or a mixture of these compounds wherein R 1 , R 2 , R 3 and R 4 are independently an alkyl group having from 1 to 20 carbon atoms, an aryl group, a cycloalkyl group having from 3 to 20 carbon atoms or an aromatic group having from 5 to 20 carbon atoms, and m and n are independently a value of from 0 to 2, is mixed with (c) saturated or unsaturated monohydric alcohol of the general formula, R 5 OH, or polyhydric alcohol and each having from 1 to 20 carbon atoms for reaction in dissolved state in the presence of (b) carbon dioxide in an inert hydrocarbon solvent to obtain component (A).
  • the magnesium alcoholate useful in the present invention includes, for example, Mg(OCH 3 ) 2 , Mg(OC 2 H 5 ) 2 , Mg(OC 3 H 7 ) 2 , Mg(OC 4 H 9 ) 2 , Mg(OCH(CH 3 )C 2 H 5 ) 2 , Mg(OC 8 H 17 ) 2 , Mg(OCH 2 CH(C 2 H 5 )C 4 H 9 ) 2 , Mg(OCH 2 CHCH 2 ) 2 , Mg(OC 6 H 5 ) 2 , Mg(OC 6 H 11 ) 2 , Mg(OC 6 H 4 CH 3 ) 2 , Mg(OC 10 H 7 ) 2 , Mg(OC 10 H 6 CH 3 ) 2 , Mg(OC 10 H 17 ) 2 , Mg(OC 10 H 16 CH 3 ) 2 , Mg(OCH 3 )(OC 2 H 5 ), Mg(OC 2 H 5 )(OC 6 H 13 ), Mg(OC
  • alkyl magnesium examples include Mg(CH 3 ) 2 , Mg(C 2 H 5 ) 2 , Mg(C 3 H 5 ) 2 , Mg(C 4 H 9 ) 2 , Mg(C 6 H 13 ) 2 , Mg(C 8 H 17 ) 2 , Mg(CHCHC 2 H 6 ) 2 , Mg(C 6 H 5 ) 2 , Mg(C 6 H 4 CH 3 ) 2 , Mg(C 6 H 11 ) 2 , Mg(C 10 H 7 ) 2 , Mg(CH 3 )(C 2 H 5 ), Mg(C 2 H 5 )(C 6 H 11 ), Mg(C 3 H 7 )(C 6 H 5 ) and the like.
  • These alkyl magnesium compounds may be used singly or in combination. Aside from these compounds, Mg(OC 2 H 5 )(C 4 H 9 ) and Mg(OC 3 H 7 )(C 6 H 5 ) may also be used.
  • the alcohols used as the ingredient (c) may be aliphatic saturated or unsaturated alcohols.
  • examples of such alcohols include methanol, ethanol, propanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol, dodecanol, propenyl alcohol, butenyl alcohol, ethylene glycol, trimethylene glycol and the like.
  • aliphatic alcohols having from 2 to 10 carbon atoms are preferred.
  • the component (A) is subjected to reaction with (d) a titanium halide of the general formula, TiX p (OR 6 ) 4-p , wherein X represents Cl or Br, R 6 represents an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms and p is an integer of from 1 to 4, and/or a vanadyl halide of the general formula, VO Xq (OR 7 ) 3-q , and/or a vanadium halide of the general formula, VX r (OR 8 ) 4-r , wherein each X represents Cl or Br, R 7 and R 8 are independently an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, q is an integer of from 1 to 3 and r is an integer of from 1 to 4, and/or a silane hal
  • This reaction is preferably carried out in an aromatic or aliphatic inert hydrocarbon solvent used in appropriate amounts.
  • Examples of the boron compound (e) include methyl borate, ethyl borate, propyl borate, isopropyl borate, butyl borate, isobutyl borate, t-butyl borate, pentyl borate, octyl borate, 4-chlorobutyl borate, aryl borate, phenyl borate, toluyl borate, diethylcyclohexyl borate, ethyldibutoxyborane, dibutylmonoethoxyborane, triisopropylborane, tributhlborane, tricyclohexylborane and the like.
  • the B/Mg ratio by mole in the boron compound and the component A used in the step B is generally in the range of 0.1/1 to 2.0/1, preferably 0.3/1 to 1/1.
  • the titanium halides of the general formula, TiX p (OR 6 ) 4-p , in (d) include titanium tetrachloride, titanium tetrabromide, titanium trichloromethoxide, titanium trichloroethoxide, titanium trichloropropoxide, titanium trichlorobutoxide, titanium trichlorohexoxide, titanium trichlorooctoxide, titanium trichlorocyclohexoxide, titanium trichlorophenoxide, titanium tribromoethoxide, titanium tribromobutoxide, titanium dichlorodiethoxide, titanium dichlorodipropoxide, titanium dichlorodibutoxide, titanium dichlorodioctoxide, titanium dichlorodiphenoxide, titanium dichlorodicyclohexoxide, titanium dibromodiethoxide, titanium dibromodibutoxide, titanium chlorotrimethoxide, titanium chlorotriethoxide, titanium chloro
  • titanium halides other than titanium tetrachloride and titanium tetrabromide can be prepared by reaction between titanium tetrahalides and ortho-titanic acid esters. In place of the compounds prepared by the above reaction, there may be used mixtures of titanium tetrahalides and ortho-titanic acid esters. Of these titanium halides, titanium tetrachloride is most preferable.
  • vanadyl halides represented by the general formula, VO Xq (OR 7 ) 3-q and vanadium halide of the general formula, VX r (OR 8 ) 4-r include, for example, vanadyl trichloride, vanadyl tribromide, vanadyl dichloroethoxide, vanadyl dichlorobutoxide, vanadyl dichlorophenoxide, vanadyl dibromomethoxide, vanadyl dibromopropoxide, vanadyl dibromocyclohexoxide, vanadyl chlorodimethoxide, vanadyl chlorodiethoxide, vanadyl chlorodicyclohexoxide, vanadyl bromodipropoxide, vanadyl bromodibutoxide, vanadium tetrachloride, vanadium tetrabromide, vanadium trichloromethoxide,
  • the silane halides (d) represented by the general formula, SiX s (OR 9 ) 4-s include silicon tetrachloride, silicon tetrabromide, silicon tribromomethoxide, silicon trichloroethoxide, silicon trichloropropoxide, silicon trichlorobutoxide, silicon trichlorocyclohexoxide, silicon dichlorodimethoxide, silicon dibromodiethoxide, silicon dichlorodipropoxide, silicon dibromodibutoxide, silicon dichlorodiphenoxide, silicon bromotrimethoxide, silicon chlorotriethoxide, silicon bromotripropoxide, silicon chlorotributoxide and the like. These compounds may be used singly or in combination.
  • the molar ratio of the total metals in the titanium halide, vanadyl halide, vanadium halide and/or silane halide used in the step B and Mg in the component A is generally in the range of 1/0.3 to 20/1, preferably from 1/0.5 to 5/1.
  • the solid product (I) is dissolved in a solvent containing a cyclic ether (f) and re-precipitated to obtain the solid product (II).
  • the carrier (solid product (II)) having a uniform shape and size of the particles can be obtained.
  • the boron compound (e) in the mother liquor of the step B.
  • the presence of the boron compound (e) at the time of the re-precipitation has been found to show a good effect of preventing the particles from shattering or crushing in a subsequent step although the reason for this is not known at the present stage.
  • cyclic ether (f) examples include tetrahydrofuran, tetrahydropyran, methyltetrahydrofuran, dimethyltetrahydropyran, tetramethyltetrahydrofuran, dioxane, dioxorane, trioxane, pyran, benzopyran, dihydrobenzofuran and the like. Of these, tetrahydrofuran is most preferred.
  • the solid product (II) is reacted with (h) a mixture of (g) the component B consisting of a titanium halide of the general formula, TiX p (OR 6 ) 4-p , a vanadyl halide of the general formula, VOX q (OR 7 ) 3-q and/or a vanadium halide of the general formula, VX r (OR 8 ) 4-r and an electron donor, to obtain solid product (III).
  • the component B consisting of a titanium halide of the general formula, TiX p (OR 6 ) 4-p , a vanadyl halide of the general formula, VOX q (OR 7 ) 3-q and/or a vanadium halide of the general formula, VX r (OR 8 ) 4-r and an electron donor, to obtain solid product (III).
  • X represents Cl or Br
  • R 6 , R 7 and R 8 independently represent an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms
  • q is an integer of from 1 to 3
  • p and r are independently an integer of from 1 to 4.
  • the solid product (II) or (III) should preferably be treated with (g) the component B.
  • the component (B) can be selected from the titanium halides, vanadyl halides and vanadium halides set forth with respect to the step B.
  • the component B may be added to the solid product (II) or (III), or the solid product (II) or (III) may be added to the component B.
  • the electron donor suitable for use in the mixture (h) are aromatic mono and poly-valent carboxylic acid esters.
  • aromatic polyvalent carboxylic acid esters include benzene polyvalent carboxylic acid esters and naphthalene polyvalent carboxylic acid esters.
  • benzene polyvalent carboxylic acid esters include: mono and diesters of benzylcarboxylic acids such as monomethyl phthalate, dimethyl phthalate, monoethyl phthalate, diethyl phthalate, dipropyl phthalate, mono-n-butyl phthalate, di-n-butyl phthalate, monoisobutyl phthalate, diisobutyl phthalate, di-n-hexyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, didecyl phthalate, dibenzyl phthalate, diphenyl phthalate, diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, di-2-ethylhexyl isophthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dioc
  • naphthalene polyvalent carboxylic acid esters include mono, di, tri, tetra and pentaesters of naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid and naphthalenepentacarboxylic acid.
  • aromatic monocarboxylic acid ester examples include benzoic acid esters with or without substituents such as methyl benzoate, ethyl benzoate, butyl benzoate, isobutyl benzoate, cyclohexyl benzoate, methyl-p-toluate, ethyl-p-toluate, methyl-p-anisate, butyl-p-anisate, ethyl chlorobenzoate, methyl bromobenzoate and the like.
  • the amount of the electron donor used in the step D is in the range of from about 0.0001 to 1.0 mole, preferably from 0.005 to 0.8 moles, per gram atom of titanium or vanadium.
  • the diluents useful in the present invention include aromatic compounds such as benzene, toluene, xylene, ethylbenzene and the like, halogenated aromatic compounds such as chlorobenzene, dibromobenzene and the like, alkanes such as hexane, heptane, octane, nonane, decane, undecane, cyclohexane, methylcyclohexane and the like, halogenated alkanes such as 1,2-dichloroethane, 1,1,2-trichloroethane, carbon tetrachloride and the like, isoparaffin hydrocarbons, kerosine, and the like.
  • aromatic compounds such as benzene, toluene, xylene, ethylbenzene and the like
  • halogenated aromatic compounds such as chlorobenzene, dibromobenzene and the like
  • alkanes such as
  • the solid product (III) is obtained by reaction between the solid product (II) and (g) the component B, which is further reacted with (h) the mixture of the component (B) and an electron donor to obtain solid product (IV) which is the catalytic component of the invention.
  • the reactions wherein the solid product (IV) is obtained through the solid product (II) may be effected in a reverse order of the reactions set forth above wherein (h) is initially reacted with the solid product (II) to obtain the solid product (III), which is subsequently reacted with (g) to obtain the solid product (IV).
  • the catalytic component or product of the invention is prepared in an inert gas such as nitrogen or argon or in an atmosphere of alpha-olefin in such a condition that catalyst poisons such as water and oxygen-carbon oxide are eliminated.
  • the purification of the diluent and starting materials used is useful for removing the catalyst poisons from the preparation system of the catalyst.
  • the solid product (IV) which is appropriately used as the catalytic component.
  • the solid product (IV) Prior to the use of the solid product (IV), it is preferred to remove unreacted starting materials from the solid product.
  • an appropriate solvent such as a liquid hydrocarbon or chlorocarbon is conveniently used to wash the solid therewith within a short time after completion of the preparation reaction. Prolonged contact between the catalytic component and unreacted starting materials may adversely influence the properties of the final catalytic component.
  • the thus obtained solid product (IV) may be in contact with at least one liquid electron acceptor prior to its use in polymerization.
  • the electron acceptors useful in the present invention should be liquid at a treating temperature and should be those having a high Lewis acidity sufficient to eliminate impurities such as unreacted starting materials and compounds not well combined from the surface of the solid product (IV).
  • Preferable electron acceptors are halides of the metals of Groups III to V of the Periodic Table which are liquid up to temperatures not higher than about 170° C.
  • the inert liquid should be substantially removed prior to the contact of the washed solid product with the electron acceptor.
  • the chemical structure of the catalytic component according to the invention has never been known at present and should preferably comprise from about 1 to about 6 wt % of titanium, from about 10 to about 25 wt % of magnesium and about 45 to about 65 wt % of a halogen.
  • a preferable catalytic component or product prepared according to the invention comprises from about 1.0 to about 3.0 wt % of titanium, from about 15 to about 21 wt % of magnesium and from about 55 to about 65 wt % of chlorine.
  • the titanium-containing catalytic component of the invention may be pre-polymerized with an alpha-olefin prior to use as a catalytic component for polymerization.
  • the catalytic component and an organic aluminum compound co-catalyst are contacted with an alpha-olefin under polymerization condition, preferably in the presence of a modifier such as a silane and in an inert hydrocarbon such as hexane.
  • the ratio by weight of the polymer and the catalyst in the pre-polymerized catalytic component is in the range of from about 0.1:1 to about 20:1.
  • a film of the polymer is formed about individual catalyst particles and can, in most case, improve the morphology, activity, stereospecificity and wear resistance of the particles.
  • the pre-polymerization procedure which is the most useful is described, for example, in U.S. Pat. No. 4,579,836 referred to in the afore-mentioned Japanese Laid-open Patent Application No. 63-54,405.
  • the titanium-containing catalytic component of the invention is used in a polymerization catalyst containing a cocatalytic component including an alkyl metal of Group II or III and typically one or more modifying compounds.
  • Useful alkyl metals of Group II or III are of the formula, MR m , wherein M is a metal of Group II or IIIA, each R represents an alkyl group having from 1 to 20 carbon atoms, and m is a valence of M.
  • organometal, M examples include magnesium, calcium, zinc, cadmium, aluminium and potassium.
  • Examples of the suitable alkyl group, R include methyl, ethyl, butyl, hexyl, decyl, tetradecyl and eicosyl.
  • alkyl metals of Group II and IIIA are those of magnesium, zinc and aluminium wherein the alkyl moiety should preferably contain from 1 to 12 carbon atoms.
  • the compounds include Mg(CH 3 ) 2 , Mg(C 2 H 5 ) 2 , Mg(C 2 H 5 )(C 4 H 9 ), Mg(C 4 H 9 ) 2 , Mg(C 6 H 13 ) 2 , Mg(C 12 H 25 ) 2 , Zn(CH 3 ) 2 , Zn(C 2 H 5 ) 2 , Zn(C 4 H 9 ) 2 , Zn(C 4 H 9 ) 2 , Zn(C 4 H 9 )(C 8 H 17 ), Zn(C 6 H 13 ) 2 , Zn(C 12 H 25 ) 2 , Al(CH 3 ) 3 , Al(C 2 H 5 ) 3 , Al(C 3 H 7 ) 3 , Al(C 4 H 9 ) 3 , Al(C 6 H 13 ) 3 and Al(C 12 H 25 ) 3 .
  • alkyl magnesium, zinc or aluminium whose alkyl moiety has from 1 to about 6 carbon atoms are used. Best results are obtained when using trialkyl aluminium wherein each alkyl moiety has from 1 to about 6 carbon atoms, and particularly, triethyl aluminium and triisobutyl aluminium.
  • the organoaluminium compounds are those compounds having one or more halogens or hydrides and include, for example, ethylaluminium dichloride, diethylaluminium chloride, ethylaluminium sesquichloride and diisobutylaluminium hydride.
  • Typical catalyst compositions comprise the supported titanium-containing compound according to the invention and an alkyl aluminium compound in combination with a modifier containing an electron donor and, preferably, also with a silane compound.
  • the atomic ratio of aluminium and titanium in this type of catalyst composition is in the range of from 10 to about 500:1, preferably from 30 to about 300:1.
  • the molar ratio of the aluminium compound and the electron donor is in the range of from about 5 to about 40:1.
  • the molar ratio of the aluminium compound and the silane compound is preferably in the range of from about 8 to about 30:1.
  • the modifier should be an electron donor and may be silanes, mineral acids, organometal chalcogenide derivatives of hydrogen sulfide, organic acids, organic acid esters and mixtures thereof.
  • organic electron donors useful as a co-catalyst modifier of the invention are organic compounds containing oxygen, silicon, nitrogen, sulfur and/or phosphorus.
  • Such compounds include organic acids, organic acid anhydrides, organic acid esters, alcohols, ethers, aldehydes, ketones, silanes, amines, amine oxides, amides, thiols, various phosphoric acid esters, amides and the like. If necessary, the organic electron donors may be used in combination.
  • Preferable organic acids and esters include benzoic acid, halo-benzoic acid, phthalic acid, isophthalic acid, terephthalic acid and alkyl esters thereof whose alkyl moiety has from 1 to 6 carbon atoms, e.g. methyl benzoate, methyl bromobenzoate, ethyl benzoate, ethyl chlorobenzoate, butyl benzoate, isobutyl benzoate, methyl anisate, ethyl anisate, methyl p-toluate, hexyl benzoate, cyclohexyl benzoate, isobutyl phthalate. These compounds give good results with respect to the activity and stereospecificity and can be conveniently used.
  • silanes used as the co-catalyst in the present invention should be alkyl, aryl and/or alkoxy-substituted silanes which have a hydrocarbon moiety having from 1 to about 20 carbon atoms.
  • aromatic silanes include diphenyldimethoxysilane, phenyltrimethoxysilane, and methylphenyldimethoxysilane.
  • Preferable aliphatic silanes include isobutyltrimethoxysilane, diisobutyldimethoxysilane, diisopropyldimethoxysilane, di-t-butyl-dimethoxysilane and t-butyltrimethoxysilane are mentioned.
  • the catalyst according to the invention is useful for use in polymerization of alpha-olefins such as ethylene and propylene and is most useful in the stereospecific polymerization of alpha-olefins having three or more carbon atoms such as, for example, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, and mixtures thereof with or without ethylene.
  • polyalpha-olefins having high crystallinity can be prepared by contacting at least one alpha-olefin with the catalytic component under polymerizing conditions.
  • Such conditions include polymerization temperature and time, a pressure of monomer, the manner of removing contaminants for the catalyst, the proper selection of a medium for polymerization in the slurry step, the type of additive for controlling the molecular weight of polymer and other conditions well known in the art.
  • the polymerization may be effected by suspension, bulk and vapor phase polymerization processes.
  • the amount of the catalyst may vary depending on the polymerization process, the size of reactor, the type of monomer to be polymerized and other factors known in the art and can be determined with reference to examples described hereinafter.
  • the catalyst of the invention is used in an amount of from about 0.2 to 0.02 mg per g of produced polymer.
  • the polymerization is carried out at a high temperature sufficient to ensure a reasonable polymerization rate and to avoid an unduly long residence time in the reactor but at a temperature which is not so high as to bring about the production of a product with a low level of stereoirregularity caused by too high a polymerization rate.
  • the polymerization temperature is generally in the range of from about 0° C. to about 120° C. and is preferably in the range of from about 20° C. to about 95° C. from the standpoint of good of catalytic properties and high production rates. More preferably, the polymerization is carried out at a temperature ranging from about 50° C. to about 80° C.
  • the polymerization of alpha-olefins according to the invention is effected at an atmospheric pressure or at a monomer pressure higher than the atmospheric pressure.
  • the pressure of monomer is in the range of about 0.550 kg/cm 2 G or (over). It will be noted that in the vapor phase polymerization, the monomer pressure must not be less than a vapor pressure of an alpha-olefin to be polymerized at the polymerization temperature.
  • the polymerization time is generally in the range of from about 0.5 to several hours in a batch process. This time corresponds to an average residence time in continuous processes.
  • the polymerization time of from about 1 hour to about 4 hours is general for the reaction in an autoclave. In the slurry process, the polymerization time can be controlled as desired.
  • the polymerization time of from about 0.5 to several hours is generally in the continuous slurry process.
  • the diluents suitable for use in the slurry polymerization process include alkanes and cycloalkanes such as pentane, hexane, heptane, n-octane, iso-octane, cyclohexane and methylcyclohexane, alkylaromatic compounds toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, n-propylbenzene, diethylbenzene and mono and di-alkylnaphthalenes, halogenated and hydrogenated aromatic compounds such as chlorobenzene, chloronaphthalene, ortho-dichlorobenzene, tetrahydronaphthalene, decahydronaphthalene and the like, high molecular weight paraffins and mixtures thereof, and other known diluents.
  • the medium for the polymerization is purified, for example, through distillation, percolation through a molecular sieve, contact with a compound capable of removing trace impurities such as an alkylaluminium compound or other means.
  • the vapor phase polymerization process which is useful for application of the catalyst of the invention includes both an agitated bed reactor system and a fluidized bed reactor system and is described, for example, in U.S. Pat. Nos. 3,957,448, 3,965,083, 3,971,768, 3,970,611, 4,129,701, 4,101,289, 3,652,527 and 4,003,712. These references are cited in the afore-indicated Japanese Laid-open Patent Application No. 63-54,405.
  • a typical vapor phase olefin polymerization reaction system is comprised of a reaction vessel wherein an olefin monomer and the catalytic component are added and which includes an agitated bed for polymer particles to be formed.
  • catalytic components are supplied at the same time or separately through one or more valve-controlled ports of the reaction vessel.
  • the olefin monomer is typically fed into the reactor through a circulation gas system wherein the monomer withdrawn as an off-gas and a fresh starting monomer are mixed and fed into the reaction vessel.
  • a quenching liquid which may be a liquid monomer may be added to an olefin being polymerized through the circulation gas system in order to control the temperature.
  • the polymerization should be effected under such conditions that oxygen, water and other substances capable of acting as a catalyst poison are eliminated.
  • the polymerization can be carried out by the use of an additive which is able to control the molecular weight of polymer.
  • an additive which is able to control the molecular weight of polymer.
  • hydrogen may be used as is well known in the art.
  • the catalyst may be contacted with water, an alcohol, acetone or other catalyst deactivators by a procedure known in the art at the time of completing or stopping the polymerization or at the time of deactivating the catalyst.
  • the product prepared according to the process of the invention is usually solid in nature and is mainly composed of an isotactic polyalpha-olefin.
  • the yield of the polymer is high relative to the amount of catalyst and can be obtained without separation of the catalytic residue.
  • the level of a stereoregular side product is significantly low and a useful product is obtained without isolation.
  • the polymer product prepared in the presence of the catalyst according to the invention can be processed into useful articles by extrusion molding, injection molding and other ordinary techniques.
  • the catalyst particles useful for polymerization of olefins are prepared under varying conditions for small and large sizes without breakage of the particles during the production process, or even if the particles are broken, the breakage can be significantly suppressed in a much smaller degree than the case using silane compounds as a shape control agent. Especially, it becomes possible to make a large-sized catalyst having a sharp size distribution.
  • the large-sized catalyst with a sharp size distribution is kept as a replica for the polymer produced by the polymerization, so that when the polymer is formed as adhesive polymer particles, the fluidity of the polymer particles is drastically improved over the case where smaller polymer particles are produced. This is well known to one skilled in the art. This is why the catalyst of the invention is very useful in preparing copolymers having a high content of rubber component by vapor phase polymerization at high operation efficiencies.
  • step A is described.
  • step A (a) a magnesium compound of the general formula, Mg(OR 1 ) n (OR 2 ) 2-n or MgR 3 m (OR 4 ) 2-m or a mixture of these compounds wherein R 1 , R 2 , R 3 and R 4 are independently an alkyl group having from 1 to 20 carbon atoms, an aryl group, a cycloalkyl group having from 3 to 20 carbon atoms or an aromatic group having from 5 to 20 carbon atoms, and m and n are independently a value of from 0 to 2, is mixed with (c) saturated or unsaturated monohydric alcohol of the general formula, R 5 OH, or polyhydric alcohol and each having from 1 to 20 carbon atoms for reaction in dissolved state in the presence of (b) carbon dioxide in an inert hydrocarbon solvent to obtain component (A).
  • the reaction is carried out at a temperature of from 10° to 200° C., preferably from 20° to 150° C., for a time of from 10 minutes to 24 hours.
  • the starting materials are charged at a normal temperature ranging from 10° to 30° C. and then heated to 40° to 150° C. to facilitate dissolution of the magnesium compound.
  • the magnesium alcoholates useful in the present invention includes, for example, Mg(OCH 3 ) 2 , Mg(OC 2 H 5 ) 2 , Mg(OC 3 H 7 ) 2 , Mg(OC 4 H 9 ) 2 , Mg(OCH(CH 3 )C 2 H 5 ) 2 , 2Mg(OC 8 H 17 ) 2 , Mg(OCH 2 CH(C 2 H 5 )C 4 H 9 ) 2 , Mg(OCH 2 CHCH 2 ) 2 , Mg(OC 6 H 5 ) 2 , Mg(OC 6 H 11 ) 2 , Mg(OC 6 H 4 CH 3 ) 2 , Mg(OC 10 H 7 ) 2 , Mg(OC 10 H 6 CH 3 ) 2 , Mg(OC 10 H 17 ) 2 , Mg(OC 10 H 16 CH 3 ) 2 , Mg(OCH 3 )(OC 2 H 5 ), Mg(OC 2 H 5 )(OC 6 H 13 ), Mg(
  • alkyl magnesium examples include Mg(CH 3 ) 2 , Mg(C 2 H 5 ) 2 , Mg(C 3 H 7 ) 2 , Mg(C 4 H 9 ) 2 , Mg(C 6 H 13 ) 2 , Mg(C 8 H 17 ) 2 , Mg(CHCHC 2 H 5 ) 2 , Mg(C 6 H 5 ) 2 , Mg(C 6 H 4 CH 3 ) 2 , Mg(C 6 H 11 ) 2 , Mg(C 10 H 7 ) 2 , Mg(CH 3 )(C 2 H 5 ), Mg(C 2 H 5 )(C 6 H 11 ),Mg(C 3 H 7 )(C 6 H 5 ) and the like.
  • These alkyl magnesium compounds may be used singly or in combination. Aside from these compounds, Mg(OC 2 H 5 )(C 4 H 9 ) and Mg(OC 3 H 7 )(C 6 H 5 ) may also be used.
  • the alcohols used as the ingredient (c) may be aliphatic saturated or unsaturated alcohols.
  • examples of such alcohols include methanol, ethanol, propanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol, dodecanol, propenyl alcohol, butenyl alcohol, ethylene glycol, trimethylene glycol and the like.
  • aliphatic alcohols having from 2 to 10 carbon atoms are preferred.
  • the component (A) is subjected to reaction with (d) a titanium halide of the general formula, TiX p (OR 6 ) 4-p , wherein X represents Cl or Br, R 6 represents an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms and p is an integer of from 1 to 4, and/or a vanadyl halide of the general formula, VX q (OR 7 ) 3-q , and/or a vanadium halide of the general formula, VX r (OR 8 ) 4-r , wherein each X represents Cl or Br, R 7 and R 8 are independently an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, q is an integer of from 1 to 3 and r is an integer of from 1 to 4, and/or a silane halide
  • This reaction is preferably carried out in an aromatic or aliphatic inert hydrocarbon solvent used in appropriate amounts.
  • the reaction may be conducted by mixing the component A with the silane compound, to which the titanium halide and/or vanadyl halide and/or vanadium halide is added.
  • the silane compound and the titanium halide and/or vanadyl halide and/or vanadium halide are first mixed, to which the component A is then added.
  • the temperature at the time of the mixing may be in the range of from -40° C. to 100° C., preferably from -10° to 50° C.
  • silane compound (e) examples include trimethylmonoethoxysilane, trimethylmonopropoxysilane, trimethylmonobutoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane, triethylmonobutoxysilane, tripropylmonoethoxysilane, tributylmonomethoxysilane, tributylmonoethoxysilane, trihexylmonoethoxysilane, cyclohexyldimethylmonoethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, cyclohexylmethyldiethoxysilane, methyltriethoxysilane, methyltripropoxysilane, e
  • the Si/Mg ratio by mole in the silane compound and the component A used in the step B is generally in the range of 0.1/1 to 2.0/1, preferably 0.3/1 to 1/1.
  • the titanium halides of the general formula, TiX p (OR 6 ) 4-p , in (d) include titanium tetrachloride, titanium tetrabromide, titanium trichloromethoxide, titanium trichloroethoxide, titanium trichloropropoxide, titanium trichlorobutoxide, titanium trichlorohexoxide, titanium trichlorooctoxide, titanium trichlorocyclohexoxide, titanium trichlorophenoxide, titanium tribromoethoxide, titanium tribromobutoxide, titanium dichlorodiethoxide, titanium dichlorodipropoxide, titanium dichlorodibutoxide, titanium dichlorodioctoxide, titanium dichlorodiphenoxide, titanium dichlorodicyclohexoxide, titanium dibromodiethoxide, titanium dibromodibutoxide, titanium chlorotrimethoxide, titanium chlorotriethoxide, titanium chloro
  • titanium halides other than titanium tetrachloride and titanium tetrabromide can be prepared by reaction between titanium tetrahalides and ortho-titanic acid esters. In place of the compound prepared by the above reaction, there may be used mixtures of titanium tetrahalides and ortho-titanic acid esters. Of these titanium halides, titanium tetrachloride is most preferable.
  • vanadyl halides represented by the general formula, VOX q (OR 7 ) 3-q and vanadium halide of the general formula, VX r (OR 8 ) 4-r include, for example, vanadyl trichloride, vanadyl tribromide, vanadyl dichloroethoxide, vanadyl dichlorobutoxide, vanadyl dichlorophenoxide, vanadyl dibromomethoxide, vanadyl dibromopropoxide, vanadyl dibromocyclohexoxide, vanadyl chlorodimethoxide, vanadyl chlorodiethoxide, vanadyl chlorodicyclohexoxide, vanadyl bromodipropoxide, vanadyl bromodibutoxide, vanadium tetrachloride, vanadium tetrabromide, vanadium trichloromethoxide,
  • the silane halides represented by the general formula, SiX s (OR 9 ) 4-s include silicon tetrachloride, silicon tetrabromide, silicon tribromomethoxide, silicon trichloroethoxide, silicon tribromopropoxide, silicon trichlorobutoxide, silicon trichlorocyclohexoxide, silicon dichlorodimethoxide, silicon dibromodiethoxide, silicon dichlorodipropoxide, silicon dibromodibutoxide, silicon dichlorodiphenoxide, silicon bromotrimethoxide, silicon chlorotriethoxide, silicon bromotripropoxide, silicon chlorotributoxide and the like. These compounds may be used singly or in combination.
  • the molar ratio of the total metals in the titanium halide, vanadyl halide, vanadium halide and/or silane halide used in the step B and Mg in the component A is generally in the range of 1/0.3 to 20/1, preferably from 1/0.5 to 5/1.
  • the solid product (I) is dissolved in a solvent containing (g) a cyclic ether and re-precipitated to obtain the solid product (II).
  • the carrier (solid product (II)) having a uniform shape and size of the particles can be obtained.
  • the alkoxysilane alkoxide (e) in the mother liquor of the step B.
  • the temperature at the time of the addition of the alcohol (f) and the cyclic ether (g) is in the range of from -40° to 100° C., preferably from -10° to 50° C. After the addition, the temperature is raised to 50° to 150° C. in 1 minute to 10 hours, preferably in 5 minutes to 5 hours, at which the content is maintained for 1 minute to 6 hours, preferably 5 minutes to 3 hours to complete the precipitation.
  • cyclic ether (g) examples include tetrahydrofuran, tetrahydropyran, methyltetrahydrofuran, dimethyltetrahydropyran, tetramethyltetrahydrofuran, dioxane, dioxorane, trioxane, pyran, benzopyran, dihydrobenzofuran and the like. Of these, tetrahydrofuran is most preferred.
  • Examples of the alcohol (f) include linear alkyl alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, hexanol, 2-ethylhexanol, octanol and the like, cyclic alkyl alcohols such as cyclopentanol, cyclohexanol and the like, diols such as 1,2-propanediol, 1,4-butanediol and the like, ethylene glycol, trimethylene glycol, propenyl alcohol, butenyl alcohol and the like.
  • linear alkyl alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, hexanol, 2-ethylhexanol,
  • linear alkyl alcohols having from 2 to 10 carbon atoms such as ethanol, propanol, isopropanol, butanol, 2-ethylhexanol and the like are most preferred.
  • the solid product (II) is reacted with (h) the component B consisting of a titanium halide of the general formula, TiX p (OR 6 ) 4-p , a vanadyl halide of the general formula, VOX q (OR 7 ) 3-q and/or a vanadium halide of the general formula, VX r (OR 8 ) 4-r , wherein each X represents Cl or Br, R 6 , R 7 and R 8 independently represent an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, q is an integer of from 1 to 3, and p and r are independently an integer of from 1 to 4, followed by further reaction with a mixture of (i) the component (B) and (j) an electron donor, thereby obtaining solid product (IV).
  • the component B consisting of a titanium halide of the general formula, TiX p (OR 6 ) 4-p ,
  • the component (B) can be selected from the titanium halides, vanadyl halides and vanadium halides set forth with respect to the step B.
  • the mixing of the solid products (II) and (III) and the component B may be carried out by charging the component B into the solid products (II) and (III) or by charging the solid products (II) and (III) into the component (B).
  • the treating temperatures for the solid products (II) and (III) in the step D are, respectively, in the range of from 40° to 200° C., preferably from 50° to 150° C. and the reaction time is in the range of from 5 minutes to 6 hours, preferably from 10 minutes to 5 hours.
  • the solid matter is separated by filtration or decantation, after which it is washed with an inert hydrocarbon solvent to remove unreacted matters or side products.
  • the washing with aromatic solvents such as toluene, benzene or xylene prior to the washing with the inert hydrocarbon solvent can further enhance the washing effect.
  • the electron donors suitable for the treatment are aromatic mono and poly-valent carboxylic acid esters.
  • aromatic polyvalent carboxylic acid esters include benzene polyvalent carboxylic acid esters and naphthalene polyvalent carboxylic acid esters.
  • benzene polyvalent carboxylic acid esters include monomethyl phthalate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, mono-n-butyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-t-butyl phthalate, di-n-hexyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diphenyl phthalate, dibenzyl phthalate and the like.
  • aromatic monocarboxylic acid ester examples include benzoic acid esters with or without substituents such as methyl benzoate, ethyl benzoate, butyl benzoate, isobutyl benzoate, cyclohexyl benzoate, methyl-p-toluate, ethyl-p-toluate, methyl-p-anisate, butyl-p-anisate, ethyl chlorobenzoate, methyl bromobenzoate and the like.
  • the electron donor used in the step D is in the range of from about 0.0001 to 1.0 mole, preferably from 0.005 to 0.8 moles, per gram atom of titanium or vanadium.
  • the diluents useful in the present invention include aromatic compounds such as benzene, toluene, xylene, ethylbenzene and the like, halogenated aromatic compounds such as chlorobenzene, dibromobenzene and the like, alkanes such as hexane, heptane, octane, nonane, decane, undecane, cyclohexane, methylcyclohexane and the like, halogenated alkanes such as 1,2-dichloroethane, 1,1,2-trichloroethane, carbon tetrachloride and the like, isoparaffin hydrocarbons, kerosine, and the like.
  • aromatic compounds such as benzene, toluene, xylene, ethylbenzene and the like
  • halogenated aromatic compounds such as chlorobenzene, dibromobenzene and the like
  • alkanes such as
  • the catalytic component or product of the invention is prepared in an inert gas such as nitrogen or argon or in an atmosphere of alpha-olefin in such a condition that catalyst poisons such as water and oxygen-carbon oxide are eliminated.
  • the purification of the diluent and starting materials used is useful for removing the catalyst poisons from the preparation system of the catalyst.
  • the solid product (IV) which is appropriately used as the catalytic component.
  • a catalyst for use in polymerization of olefins which is in the form of particles having a large size and which has a good crystal form.
  • the particles suffer little or no breakage, so that a large-sized catalyst with a sharp size distribution can be obtained.
  • the large-sized catalyst with a sharp size distribution is kept as a replica for the polymer produced by the polymerization, so that when the polymer is formed as adhesive polymer particles, the fluidity of the polymer particles is drastically improved over the case where smaller polymer particles are produced. This is well known to one skilled in the art. This is why the catalyst of the invention is very useful in preparing copolymers having a high content of rubber component by vapor phase polymerization at high operation efficiencies.
  • step A is described.
  • step A (a) a magnesium compound of the general formula, Mg(OR 1 ) n (OR 2 ) 2-n or MgR 3 m (OR 4 ) 2-m or a mixture of these compounds wherein R 1 , R 2 , R 3 and R 4 are independently an alkyl group having from 1 to 20 carbon atoms, an aryl group, a cycloalkyl group having from 3 to 20 carbon atoms or an aromatic group having from 5 to 20 carbon atoms, and m and n are independently a value of from 0 to 2, is mixed with (c) saturated or unsaturated monohydric alcohol of the general formula, R 5 OH, or polyhydric alcohol and each having from 1 to 20 carbon atoms for reaction in dissolved state in the presence of (b) carbon dioxide in an inert hydrocarbon solvent to obtain component (A).
  • the reaction is carried out at a temperature of from 10 to 200° C., preferably from 20° to 150° C., for a time of from 10 minutes to 24 hours.
  • the starting materials are charged at a normal temperature ranging from 10° to 30° C. and then heated to 40° to 150° C. to facilitate dissolution of the magnesium compound.
  • the magnesium alcoholates useful in the present invention includes, for example, Mg(OCH 3 ) 2 , Mg(OC 2 H 5 ) 2 , Mg(OC 3 H 7 ) 2 , Mg(OC 4 H 9 ) 2 , Mg(OCH(CH 3 )C 2 H 5 ) 2 , 2Mg(OC 8 H 17 ) 2 , Mg(OCH 2 CH(C 2 H 5 )C 4 H 9 ) 2 , Mg(OCH 2 CHCH 2 ) 2 , Mg(OC 6 H 5 ) 2 , Mg(OC 6 H 11 ) 2 , Mg(OC 6 H 4 CH 3 ) 2 , Mg(OC 10 H 7 ) 2 , Mg(OC 10 H 6 CH 3 ) 2 , Mg(OC 10 H 17 ) 2 , Mg(OC 10 H 16 CH 3 ) 2 , Mg(OCH 3 )(OC 2 H 5 ), Mg(OC 2 H 5 )(OC 6 H 13 ), Mg(
  • alkyl magnesium examples include Mg(CH 3 ) 2 , Mg(C 2 H 5 ) 2 , Mg(C 3 H 7 ) 2 , Mg(C 4 H 9 ) 2 , Mg(C 6 H 13 ) 2 , Mg(C 8 H 17 ) 2 , Mg(CHCHC 2 H 5 ) 2 , Mg(C 6 H 5 ) 2 , Mg(C 6 H 4 CH 3 ) 2 , Mg(C 6 H 11 ) 2 , Mg(C 10 H 7 ) 2 , Mg(CH 3 )(C 2 H 5 ), Mg(C 2 H 5 )(C 6 H 11 ), Mg(C 3 H 7 )(C 6 H 5 ) and the like.
  • These alkyl magnesium compounds may be used singly or in combination. Aside from these compounds, Mg(OC 2 H 5 )(C 4 H 9 ) and Mg(OC 3 H 7 )(C 6 H 5 ) may also be used.
  • the alcohols used as the ingredient (c) may be aliphatic saturated or unsaturated alcohols.
  • examples of such alcohols include methanol, ethanol, propanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol, dodecanol, propenyl alcohol, butenyl alcohol, ethylene glycol, trimethylene glycol and the like.
  • aliphatic alcohols having from 2 to 10 carbon atoms are preferred.
  • the component (A) is subjected to reaction with (d) a titanium halide of the general formula, TiX p (OR 6 ) 4-p , wherein X represents Cl or Br, R 6 represents an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms and p is an integer of from 1 to 4, and/or a vanadyl halide of the general formula, VOX q (OR 7 ) 3-q , and/or a vanadium halide of the general formula, VX r (OR 8 ) 4-r , wherein each X represents Cl or Br, R 7 and R 8 are independently an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, q is an integer of from 1 to 3 and r is an integer of from 1 to 4, and/or a silane hal
  • This reaction is preferably carried out in an aromatic or aliphatic inert hydrocarbon solvent used in appropriate amounts.
  • the reaction may be conducted by mixing the component A with the boron compound, to which the titanium halide and/or vanadyl halide and/or vanadium halide is added.
  • the boron compound and the titanium halide and/or vanadyl halide and/or vanadium halide are first mixed, to which the component A is then added.
  • the temperature at the time of the mixing may be in the range of from -40° C. to 100° C., preferably from -10° to 50° C.
  • Examples of the boron compound (e) include methyl borate, ethyl borate, propyl borate, isopropyl borate, butyl borate, isobutyl borate, t-butyl borate, pentyl borate, octyl borate, 4-chlorobutyl borate, aryl borate, phenyl borate, toluyl borate, diethylcyclohexyl borate, ethyldibutoxyborane, dibutylmonoethoxyborane, triethyl borane, triisopropylborane, tributylborane, tricyclohexylborane and the like.
  • the B/Mg ratio by mole in the boron compound and the component A used in the step B is generally in the range of 0.1/1 to 2.0/1, preferably 0.3/1 to 1/1.
  • the titanium halides of the general formula, TiX p (OR 6 ) 4-p , in (d) include titanium tetrachloride, titanium tetrabromide, titanium trichloromethoxide, titanium trichloroethoxide, titanium trichloropropoxide, titanium trichlorobutoxide, titanium trichlorohexoxide, titanium trichlorooctoxide, titanium trichlorocyclohexoxide, titanium trichlorophenoxide, titanium tribromoethoxide, titanium tribromobutoxide, titanium dichlorodiethoxide, titanium dichlorodipropoxide, titanium dichlorodibutoxide, titanium dichlorodioctoxide, titanium dichlorodiphenoxide, titanium dichlorodicyclohexoxide, titanium dibromodiethoxide, titanium dibromodibutoxide, titanium chlorotrimethoxide, titanium chlorotriethoxide, titanium chloro
  • titanium halides other than titanium tetrachloride and titanium tetrabromide can be prepared by reaction between titanium tetrahalides and ortho-titanic acid esters. In place of the compounds prepared by the above reaction, there may be used mixtures of titanium tetrahalides and ortho-titanic acid esters. Of these titanium halides, titanium tetrachloride is most preferable.
  • vanadyl halides represented by the general formula, VOX q (OR 7 ) 3-q and vanadium halide of the general formula, VX r (OR 8 ) 4-r include, for example, vanadyl trichloride, vanadyl tribromide, vanadyl dichloroethoxide, vanadyl dichlorobutoxide, vanadyl dichlorophenoxide, vanadyl dibromomethoxide, vanadyl dibromopropoxide, vanadyl dibromocyclohexoxide, vanadyl chlorodimethoxide, vanadyl chlorodiethoxide, vanadyl chlorodicyclohexoxide, vanadyl bromodipropoxide, vanadyl bromodibutoxide, vanadium tetrachloride, vanadium tetrabromide, vanadium trichloromethoxide,
  • the silane halides represented by the general formula, SiX s (OR 9 ) 4-s include silicon tetrachloride, silicon tetrabromide, silicon tribromomethoxide, silicon trichloroethoxide, silicon tribromoropropoxide, silicon trichlorobutoxide, silicon trichlorocyclohexoxide, silicon dichlorodipropoxide, silicon dibromodibutoxide, silicon dichlorodiphenoxide, silicon bromotrimethoxide, silicon chlorotriethoxide, silicon bromotripropoxide, silicon chlorotributoxide and the like. These compounds may be used singly or in combination.
  • the molar ratio of the total metals in the titanium halide, vanadyl halide, vanadium halide and/or silane halide used in the step B and Mg in the component A is generally in the range of 1/0.3 to 20/1, preferably from 1/0.5 to 5/1.
  • the solid product (I) is dissolved in a solvent containing (g) a cyclic ether and re-precipitated to obtain the solid product (II).
  • the carrier (solid product (II)) having a uniform shape and size of the particles can be obtained.
  • the boron compound (e) in the mother liquor of the step B. The presence of the boron compound at the time of the re-precipitation has been found to show a good effect of preventing the particles from shattering or crushing in a subsequent step although the reason for this is not known at the present stage.
  • the temperature at the time of the addition of the alcohol (f) and the cyclic ether (g) is in the range of from -40° to 100° C., preferably from -10° to 50° C. After the addition, the temperature is raised to 50° to 150° C. in 1 minute to 10 hours, preferably in 5 minutes to 5 hours, at which the content is maintained for 1 minute to 6 hours, preferably 5 minutes to 3 hours to complete the precipitation.
  • cyclic ether (g) examples include tetrahydrofuran, tetrahydropyran, methyltetrahydrofuran, dimethyltetrahydropyran, tetramethyltetrahydrofuran, dioxane, dioxorane, trioxane, pyran, benzopyran, dihydrobenzofuran and the like. Of these, tetrahydrofuran is most preferred.
  • Examples of the alcohol (f) include linear alkyl alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, hexanol, 2-ethylhexanol, octanol and the like, cyclic alkyl alcohols such as cyclopentanol, cyclohexanol and the like, diols such as 1,2-propanediol, 1,4-butanediol and the like, ethylene glycol, trimethylene glycol, propenyl alcohol, butenyl alcohol and the like.
  • linear alkyl alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, hexanol, 2-ethylhexanol,
  • linear alkyl alcohols having from 2 to 10 carbon atoms such as ethanol, propanol, isopropanol, butanol, 2-ethylhexanol and the like are most preferred.
  • the solid product (II) is reacted with (h) the component B consisting of a titanium halide of the general formula, TiX p (OR 6 ) 4-p , a vanadyl halide of the general formula, VOX q (OR 7 ) 3-q and/or a vanadium halide of the general formula, VX r (OR 8 ) 4-r , wherein each X represents Cl or Br, R 6 , R 7 and R 8 independently represent an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, q is an integer of from 1 to 3, and p and r are independently an integer of from 1 to 4, followed by further reaction with a mixture of (i) the component (B) and (j) an electron donor, thereby obtaining solid product (IV).
  • the component B consisting of a titanium halide of the general formula, TiX p (OR 6 ) 4-p ,
  • the component (B) can be selected from the titanium halides, vanadyl halides and vanadium halides set forth with respect to the step B.
  • the mixing of the solid products (II) and (III) and the component B may be carried out by charging the component B into the solid products (II) and (III) or by charging the solid products (II) and (III) into the component (B).
  • the treating temperatures for the solid products (II) and (III) in the step D are, respectively, in the range of from 40° to 200° C., preferably from 50° to 150° C. and the reaction time is in the range of from 5 minutes to 6 hours, preferably from 10 minutes to 5 hours.
  • the solid matter is separated by filtration or decantation, after which it is washed with an inert hydrocarbon solvent to remove unreacted matters or side products.
  • the washing with aromatic solvents such as toluene, benzene or xylene prior to the washing with the inert hydrocarbon solvent can further enhance the washing effect.
  • the electron donors suitable for the treatment are aromatic mono and poly-valent carboxylic acid esters.
  • aromatic polyvalent carboxylic acid esters include benzene polyvalent carboxylic acid esters and naphthalene polyvalent carboxylic acid esters.
  • Specific examples of the benzene polyvalent carboxylic acid esters include monomethyl phthalate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, mono-n-butyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-t-butyl phthalate, di-n-hexyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diphenyl phthalate, dibenzyl phthalate and the like.
  • aromatic monocarboxylic acid ester examples include benzoic acid esters with or without substituents such as methyl benzoate, ethyl benzoate, butyl benzoate, isobutyl benzoate, cyclohexyl benzoate, methyl-p-toluate, ethyl-p-toluate, methyl-p-anisate, ethyl-p-anisate, butyl-p-anisate, ethyl chlorobenzoate, methyl bromobenzoate and the like.
  • the electron donor used in the step D is in the range of from about 0.0001 to 1.0 mole, preferably from 0.005 to 0.8 moles, per gram atom of titanium or vanadium.
  • the diluents useful in the present invention include aromatic compounds such as benzene, toluene, xylene, ethylbenzene and the like, halogenated aromatic compounds such as chlorobenzene, dibromobenzene and the like, alkanes such as hexane, heptane, octane, nonane, decane, undecane, cyclohexane, methylcyclohexane and the like, halogenated alkanes such as 1,2-dichloroethane, 1,1,2-trichloroethane, carbon tetrachloride and the like, isoparaffin hydrocarbons, kerosine, and the like.
  • aromatic compounds such as benzene, toluene, xylene, ethylbenzene and the like
  • halogenated aromatic compounds such as chlorobenzene, dibromobenzene and the like
  • alkanes such as
  • the catalytic component or product of the invention is prepared in an inert gas such as nitrogen or argon or in an atmosphere of alpha-olefin in such a condition that catalyst poisons such as water and oxygen-carbon oxide are eliminated.
  • the purification of the diluent and starting materials used is useful for removing the catalyst poisons from the preparation system of the catalyst.
  • the solid product (IV) which is appropriately used as the catalytic component.
  • a catalyst for use in polymerization of olefins which is in the form of particles having a large size and which has a good crystal form.
  • the particles suffer little or no breakage, so that a large-sized catalyst with a sharp size distribution can be obtained.
  • the large-sized catalyst with a sharp size distribution is kept as a replica for the polymer produced by the polymerization, so that when the polymer is formed as adhesive polymer particles, the fluidity of the polymer particles is drastically improved over the case where smaller polymer particles are produced. This is well known to one skilled in the art. This is why the catalyst of the invention is very useful in preparing copolymers having a high content of rubber component by vapor phase polymerization at high operation efficiencies.
  • the catalytic ingredient or system according to the invention of the fourth aspect is obtained by the procedure described above. This procedure is described in detail according to the steps involved therein.
  • the reaction is carried out at a temperature of from 10° to 200° C., preferably from 20° to 150° C., for a time of from 10 minutes to 24 hours.
  • the starting materials are charged at room temperature ranging from 10° to 30° C. and then heated to 40° to 150° C. in order to facilitate dissolution of the magnesium compound or compounds.
  • the magnesium alcoholates useful in the present invention include, for example, Mg(OCH 3 ) 2 , Mg(OC 2 H 5 ) 2 , Mg(OC 3 H 7 ) 2 , Mg(OC 4 H 9 ) 2 , Mg(OCH(CH 3 )C 2 H 5 ) 2 , 2Mg(OC 8 H 17 ) 2 , Mg(OCH 2 CH(C 2 H 6 )C 4 H 9 ) 2 , Mg(OCH 2 CHCH 2 ) 2 , Mg(OC 6 H 6 ) 2 , Mg(OC 6 H 11 ) 2 , Mg(OC 6 H 4 CH 3 ) 2 , Mg(OC 10 H 7 ) 2 , Mg(OC 10 H 6 CH 3 ) 2 , Mg(OC 10 H 17 ) 2 , Mg(OC 10 H 16 CH 3 ) 2 , Mg(OCH 3 )(OC 2 H 5 ), Mg(OC 2 H 5 )(OC 6 H 13 ), Mg(
  • alkyl magnesium examples include Mg(CH 3 ) 2 , Mg(C 2 H 5 ) 2 , Mg(C 3 H 7 ) 2 , Mg(C 4 H 9 ) 2 , Mg(C 6 H 13 ) 2 , Mg(C 8 H 17 ) 2 , Mg(CHCHC 2 H 5 ) 2 , Mg(C 6 H 5 ) 2 , Mg(C 6 H 4 CH 3 ) 2 , Mg(C 6 H 11 ) 2 , Mg(C 10 H 7 ) 2 , Mg(CH 3 )(C 2 H 5 ), Mg(C 2 H 5 )(C 6 H 11 ), Mg(C 3 H 7 )(C 6 H 5 ) and the like. These compounds may be used singly or in combination. In addition, Mg(OC 2 H 5 )(C 4 H 9 ) and Mg(OC 3 H 7 )(C 6 H 5 ) may also be used.
  • the alcohols used as the ingredient (c) may be aliphatic saturated and unsaturated alcohols.
  • the alcohol include methanol, ethanol, propanol, iso-propanol, iso-butanol, tertiary butanol, octanol, 2-ethylhexanol, cyclohexanol, dodecanol, propenyl alcohol, butenyl alcohol, ethylene glycol, trimethylene glycol and the like.
  • aliphatic alcohols having from 2 to 10 carbon atoms are preferred.
  • step B the ingredient A is reacted, in the presence of (e) a siloxane compound having the Si--O--Si bond or a mixture of the siloxane compound and a silane compound of the general formula, R 10 t Si(OR 11 ) 4-t , wherein R 10 and R 11 independently represent an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, and t is a value of from 0 to 4, with (d) a titanium halide of the general formula, TiX p (OR 6 ) 4-p wherein X represents Cl or Br, R 6 represents an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, and p is a value of from 1 to 4, and/or a vanadyl halide of the general formula, VOX q (OR 7 ) 3-
  • reaction should preferably be carried out in an aromatic or aliphatic inert hydrocarbon solvent used in appropriate amounts.
  • the mixing order for the reaction may be such that the ingredient A and the siloxane compound or its mixture with the silane compound are first mixed, with which there is mixed the titanium halide and/or vanadyl halide and/or vanadium halide, it is preferred that the siloxane compound is mixed with the titanium halide and/or vanadyl halide and/or vanadium halide, to which the ingredient A is added.
  • the temperature during the mixing may be in the range of from -40° C. to 100° C. and is preferably in the range of from -10° C. to 50° C.
  • siloxane compound (e) examples include linear polysiloxanes of the general formula, R 3 Si-(OSiR 2 ) n -OSiR 3 , wherein R represents an alkyl group having from 1 to 20 carbon atoms, an aryl group, a cycloalkyl group or an aromatic group, and n is a value of from 1 to 10 3 , such as hexamethyldisiloxane, hexaethyldisiloxane, hexabutyrodisiloxane, octamethyltrisiloxane, octaethyltrisiloxane and the like, polyalkylalkoxysiloxanes having an alkoxy group or groups at part thereof such as hexamethyl-1,5-diethoxytrisiloxane, hexaethyl-1,5-dimethoxytrisiloxane and the like, polyalkoxyalkylsiloxanes
  • silane compound used by mixing with the above-mentioned siloxane compounds examples include trimethylmonoethoxysilane, trimethylmonopropoxysilane, trimethylmonobutoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane, triethylmonobutoxysilane, tripropylmonoethoxysilane, tributylmonomethoxysilane, tributylmonoethoxysilane, trihexylmonoethoxysilane, cyclohexyldimethylmonoethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, cyclohexylmethyldiethoxysilane, methyltriethoxysilane
  • the molar ratio of Si/Mg in the siloxane compound or its mixture with the silane compound and the ingredient A used in the step B is generally in the range of 1 to 2.0:1, preferably 0.3:1 to 1:1.
  • the titanium halides (d) of the general formula, TiX p (OR 6 ) 4-p include, for example, titanium tetrachloride, titanium tetrabromide, titanium trichloride methoxide, titanium trichloride ethoxide, titanium trichloride propoxide, titanium trichloride butoxide, titanium trichloride hexoxide, titanium trichloride octoxide, titanium trichloride cyclohexoxide, titanium trichloride phenoxide, titanium dichloride diethoxide, titanium dichloride dipropoxide, titanium dichloride dibutoxide, titanium dichloride dioctoxide, titanium dichloride diphenoxide, titanium dichloride dicyclohexoxide, titanium dibromide diethoxide, titanium dibromide dibutoxide, titanium chloride tributoxide, titanium chloride triphenoxide, titanium bromide triethoxide, titanium bromide triphenoxid
  • titanium halides other than titanium tetrachloride and titanium tetrabromide can be prepared by reaction between titanium tetrahalides and orthotitanic acid esters. In place of those products obtained by the above reaction, mixtures of titanium tetrahalides and ortho-titanic acid esters may be used in the practice of the invention. Of these, titanium tetrachloride is most preferred.
  • vanadyl halides and vanadium halides examples include vanadyl trichloride, vanadyl tribromide, vanadyl dichloride ethoxide, vanadyl dibromide methoxide, vanadyl dichloride ethoxide, vanadyl dichloride butoxide, vanadyl trichloride phenoxide, vanadyl dibromide methoxide, vanadyl dibromide propoxide, vanadyl dibromide cyclohexoxide, vanadyl chloride dimethoxide, vanadyl chloride diethoxide, vanadyl chloride dicyclohexoxide, vanadyl bromide dipropoxide, vanadyl bromide dibut
  • Examples of the halogenated silanes (d) of the general formula, SiX s (OR 9 ) 4-s include silicon tetrachloride, silicon tetrabromide, silicon tribromide methoxide, silicon trichloride ethoxide, silicon tribromide propoxide, silicon trichloride butoxide, silicon trichloride cyclohexoxide, silicon dichloride dimethoxide, silicon dibromide diethoxide, silicon dichloride dipropoxide, silicon dibromide dibutoxide, silicon dichloride diphenoxide, silicon bromide trimethoxide, silicon chloride triethoxide, silicon bromide tripropoxide, silicon chloride tributoxide, and the like. These may be used singly or in combination.
  • the molar ratio of the metals in total in the titanium halide or/and vanadyl halide or/and vanadium halide or/and halogenated silane and Mg in the ingredient A used in the step B is generally in the range of 1:0.3 to 20:1, preferably 1:0.5 to 5:1.
  • the solid product (I) obtained in the step B is dissolved in a solvent containing the cyclic ether (g) and re-precipitated to obtain solid product (II). Part or all of the solid product is dissolved and re-precipitated to obtain a carrier (solid product (II)) having uniform particle shape and size.
  • the siloxane compound (e) contained in the mother liquor of the step B exists in the mother liquor for the precipitation in the step C.
  • the alcohol (f) may be added to the suspension containing the solid product (I), after which the cyclic ether (g) is added. Alternatively, the alcohol and cyclic ether are added at the same time. As a result, there can be obtained the carrier particles (solid product (II)) with a large size.
  • the temperature at which the alcohol (f) and cyclic ether (g) are added is in the range of from -40° to 100° C., preferably from -10° to 50° C. After the addition, the temperature is raised to 50° to 150° C. in 1 minute to 10 hours, preferably 5 minutes to 5 hours, at which the reaction system is kept for 1 minute to 6 hours, preferably from 5 minutes to 3 hours, thereby completing the precipitation.
  • cyclic ether (g) examples include tetrahydrofuran, tetrahydropyran, methyltetrahydrofuran, dimethyltetrahydropyran, tetramethyltetrahydrofuran, dioxane, dioxorane, trioxane, pyran, benzopyran, dihydrobenzofuran and the like. Of these, tetrahydrofuran is most preferred.
  • the alcohol examples include linear alkyl alcohols such as methanol, ethanol, n-propanol, iso-propanol, butanol, iso-butanol, tertiary butanol, pentanol, hexanol, 2-ethylhexanol, octanol and the like, cyclic alkyl alcohols such as cyclopentanol, cyclohexanol and the like, diols such as 1,2-propanediol, 1,4-butanediol and the like, ethylene glycol, trimethylene glycol, propenyl alcohol, butenyl alcohol and the like.
  • linear alkyl alcohols such as methanol, ethanol, n-propanol, iso-propanol, butanol, iso-butanol, tertiary butanol, pentanol, hexanol, 2-ethylhex
  • a linear alkyl alcohol having from 2 to 10 carbon atoms such as ethanol, propanol, butanol, 2-ethylhexanol or the like, is most preferred.
  • the solid product (II) the solid product (II) is reacted with (h) the ingredient B including the titanium halide of the general formula, TiX p (OR 6 ) 4-p , and/or the vanadyl halide of the general formula, VOX q (OR 7 ) 3-q , and/or the vanadium halide of the general formula, VOX r (OR 8 ) 4-r , wherein each X represents Cl or Br, R 6 , R 7 and R 8 independently represent an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, q is a value of from 1 to 3 and p and r are, respectively, a value of from 1 to 4 and further reacted with a mixture of the ingredient B (i) and an electron donative material or compound (j) to obtain solid product (IV).
  • the ingredient B can be selected from the titanium halide, vanadyl halide and vanadium halide described with respect to the step B.
  • the mixing of the solid products (II) and (III) and the ingredient B may be effected by adding the ingredient B to the solid products (II) and (III) or by adding the solid products (II) and (III) to the ingredient B.
  • the treating temperatures of the solid products (II) and (III) in the step D may be in the range of from 40° to 200° C., preferably from 50° to 150° C. for each case.
  • the reaction time for both products is in the range of from 5 minutes to 6 hours, preferably from 10 minutes to 5 hours.
  • the resultant solid product is separated by filtration or decantation, after which it is washed with an inert hydrocarbon solvent to remove unreacted compounds or side products therefrom.
  • the washing effect may be further facilitated by washing the product with an aromatic solvent such as toluene, benzene, xylene or the like prior to the washing with the inert hydrocarbon solvent.
  • the electron donative compounds suitable for the above treatment include aromatic mono- and polycarboxylic acid esters.
  • Examples of the polycarboxylic acid esters include benzene polycarboxylic acid esters, naphthalene polycarboxylic acid esters and the like.
  • benzene polycarboxylic acid esters such as monomethyl phthalate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, mono-n-butyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-tert-butyl phthalate, di-n-hexyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diphenyl phthalate, dibenzyl phthalate and the like, and aromatic monocarboxylic acid esters such as benzoates with or without a substituent, e.g.
  • the electron donative compounds used in the step D is used in an amount of about 0.0001 to 1.0 mole, preferably from 0.005 to 0.8 moles, per gram atom of titanium or vanadium.
  • the diluents useful in the present invention are, for example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and the like, halogenated aromatic hydrocarbons such as chlorobenzene, dibromobenzene and the like, alkanes such as hexane, heptane, octane, nonane, decane, undecane, cyclohexane, methylcyclohexane and the like, halogenated alkanes such as 1,2-dichloroethane, 1,1,2-trichloroethane, carbon tetrachloride and the like, iso-paraffin hydrocarbons, kerosine, and the like.
  • aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and the like
  • halogenated aromatic hydrocarbons such as chlorobenzene, dibromobenz
  • the catalytic ingredient is prepared in an atmosphere of an inert gas such as nitrogen or argon gas or an alpha-olefin under conditions where catalyst poisons such as water, oxygen-carbon oxide and the like are eliminated.
  • the diluent and the starting materials used should favorably be purified in order to remove catalyst poisons from the preparation system for the catalyst.
  • the solid product (IV) which is suitable for use as the catalytic ingredient can thus be obtained.
  • the catalyst in the form of particles which have a large size suitable for use in polymerization of olefins can be obtained while keeping a good crystal shape without breakage of the particles into finer powder during the production process or with a very reduced degree of the breakage, if any.
  • a large-sized catalyst having a sharp size distribution can be obtained.
  • the large-sized catalyst with a sharp size distribution is advantageous in that the catalyst particles are kept as a replica for polymer particles produced by the polymerization.
  • the particles of polymer which are adhesive in nature are large in size, the flowability is drastically improved over that in the case where small-sized catalyst particles are used.
  • the large-sized catalyst particles are very useful in preparing copolymers having a high content of rubber component by vapor phase polymerization in a high operation efficiency.
  • reaction steps (A) through (D) described hereinabove are summarized in the FIG. 4 wherein the respective starting compounds are particularly shown.
  • the mixture was heated at 90° C. for 3 hours in an atmosphere of carbon dioxide at 2 kg/cm 2 G while agitating at 500 r.p.m.
  • the resultant solution was cooled and, after purging of the carbon dioxide gas, was handled under an atmospheric pressure.
  • the solution contained 0.1 g/ml of magnesium ethoxide.
  • THF tetrahydrofuran
  • 50 ml of tetrahydrofuran (THF) was added to the precipitated solution by the use of a syringe. While agitating at 300 r.p.m., the content was heated to 60° C. within 15 minutes. The precipitated particles were dissolved in the THF solution and re-precipitation started within 15 minutes and formation of solid matter completed within 10 minutes. After the agitation continued at 60° C. for 45 minutes, the agitation was stopped to cause solid product (II) to be precipitated. The supernatant liquid was removed by decantation and the resultant solid product (II) was washed twice with 200 ml of toluene.
  • THF tetrahydrofuran
  • the size distribution of the polymer powder was 1.2% for >2000 ⁇ , 45.9% for 1000-2000 ⁇ , 27.7% for 710-1000 ⁇ , 9.5% for 500-710 ⁇ , 2.8% for 350-500 ⁇ , 0.1% for 250-350 ⁇ , 0% for 149-210%, and 0.1% for ⁇ 149 ⁇ , with an average size particle being 1084 ⁇ .
  • Example 1 The general procedure of Example 1 was repeated except that the solution in the step A of Example 1 was used in an amount of 114 ml, 100 ml of toluene, 100 ml of chlorobenzene and 15 ml of tri-n-butyl borate were used in step B, 60 ml of THF was used in the step C, and in the step D, 200 ml of TiCl 4 was used for the third treatment with TiCl 4 and the system was maintained at 135° C. for 1 hour, thereby obtaining 13.1 g of solid product (IV).
  • the average particle size of the solid product (IV) was 35.2 ⁇ with particles having a size not larger than 5 ⁇ being contained in an amount of 5.0%.
  • Example 1 The general procedure of Example 1 was repeated except that a one liter autoclave was used for the reactions of the step B and subsequent steps, 170 ml of the solution in the step A of Example 1 was used in the step B, 200 ml of toluene and 24 ml of tri-n-butoxy borane were used in the step B, that 70 ml of THF was used in the step C and the steps of from B to C were effected while agitating at 400 r.p.m. at a pressure of carbon dioxide controlled at 3 kg/cm 2 G, and that for the second TiCl 4 treatment in the step D, 2.1 ml of diisobutyl phthalate was used instead of the di-n-butyl phthalate.
  • the yield of the solid product (IV) was 20.0 g and an average size of 31.8 ⁇ with particles having a size not larger than 5 ⁇ being 3.7%.
  • the analytical values of the solid product were found to be 18.1% of Mg, 2.2% of Ti, 56.0% of Cl, and 8.4% of diisobutyl phthalate.
  • Example 1 The general procedure of Example 1 was repeated except that 150 ml of the solution obtained in the step A of Example 1 was used in the step B along with 100 ml of toluene, 100 ml of chlorobenzene and 24 ml of triisopropyl borate, and that in the step C, 60 ml of THF was used.
  • the resultant solid product (IV) had an average size of 27.2 ⁇ and particles having a size of not larger 5 ⁇ were 3.1% in amount.
  • Example 1 The general procedure of Example 1 was repeated except that 114 ml of the solution obtained in the step A of Example 1 was used along with 60 ml of iso-paraffin (Isober G) and 14 ml of TiCl 4 , that 27 ml of THF was used in the step C and that the TiCl 4 treatment in the step D was effected in two stages and the third washing with TiCl 4 was not effected.
  • iso-paraffin iso-paraffin
  • Example 1 The general procedure of Example 1 was repeated except that 286 g of magnesium propoxide was used in the step A in place of magnesium ethoxide along with 383 g of 2-ethyl-1-hexanol was used.
  • the slurry after the reaction was transferred under nitrogen sealing conditions to a 5 liter filter equipped with an agitator, a condenser, a thermometer and a nitrogen sealing line and having a heating jacket and a filter unit at the bottom thereof, and subjected to filtration, followed by washing twice with 500 ml of toluene.
  • the analysis of the solid product (IV) revealed 18.6% of Mg, 2.1% of Ti, and 6.6% of di-n-butyl phthalate.
  • the average particle size of the solid product (IV) was 42.1 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 2.2%.
  • Example 1 The general procedure of Example 1 was repeated except that in the step B, the boron compound was not used, thereby obtaining 14.3 g of solid product (IV). In this case, a long time was required for precipitation by decantation from the step C to the step D, thus part of fine particles being lost. As shown in Table 1, fine powder was contained in very large amounts in the solid product (IV).
  • Example 1 The general procedure of Example 1 was repeated except that 20 ml of tetraethoxysilane was used instead of the boron compound in the step B, thereby obtaining 17.1 g of solid product (IV).
  • the size distribution of the resultant solid product is shown in Table 1.
  • Example 4 The general procedure of Example 4 was repeated except that in the step B of Example 4, 20 ml of trimethylchlorosilane was used instead of the boron compound.
  • Example 1 The general procedure of Example 1 was repeated except that 2 ml of tri-n-borane was used along with 18 ml of tri-n-butyl borate was used, thereby obtaining 17.3 g of solid product (IV).
  • the solid product had an average particle size of 33 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 5.1%.
  • Example 1 The general procedure of Example 1 was repeated except that 60 ml of tetrahydropyran was used instead of 50 ml of THF in the step C of Example 1, thereby obtaining 17.3 g of solid product (IV).
  • the solid product had an average particle size of 25.1 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 7.2%.
  • Example 1 The general procedure of Example 1 was repeated except that 24 ml of isobutyl borate was used instead of 20 ml of n-butyl borate and 60 ml of 2-methyltetrahydrofuran was used instead of 50 ml of THF in the step C of Example 1, thereby obtaining 17.5 g of solid product (IV).
  • the solid product had an average particle size of 28.4 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 5.9%.
  • Example 9 The general procedure of Example 9 was repeated except that 20 ml of tetraethoxysilane was used instead of the boron compound, thereby obtaining 16.3 g of solid product (IV).
  • the solid product contained a large amount of fine powder and the content of the particles having a size not larger than 5 ⁇ was >25%.
  • Example 10 The general procedure of Example 10 was repeated except that 20 ml of trimethylethoxysilane was used instead of the boron compound in the step B of Example 10, thereby obtaining 16.4 g of solid product (IV).
  • the solid product had an average particle size of 16.4 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 13%.
  • the catalysts (solid products (IV)) obtained in Examples 8 to 10 and Comparative Examples 4 to 5 were used for carrying out hexane slurry polymerization of propylene.
  • the catalyst obtained in Example 2 was used to carry out bulk polymerization.
  • the yield of the polymer was 180 g and the content of ethylene in the polymer was 10.3%.
  • the present invention of the second aspect is more particularly described by way of examples.
  • the mixture was heated at 90° C. for 3 hours in an atmosphere of carbon dioxide at 3 kg/cm 2 G while agitating at 500 r.p.m.
  • the resultant solution was cooled and, after purging of the carbon dioxide gas, was handled under an atmospheric pressure.
  • the solution contained 0.1 g/ml of magnesium ethoxide.
  • solid product (IV) 9.7 g in total of solid product (IV) was collected.
  • the solid product (IV) was found to contain 18.4% of magnesium, 2.2% of titanium, 58.6% of chlorine and 11.6% of di-n-butyl phthalate.
  • the average size of the solid product (IV) was 42.6 ⁇ with particles having a size of not larger than 5 ⁇ being 0.3%.
  • the size distribution of the polymer powder is shown in Table 5.
  • Example 14 The general procedure of Example 14 was repeated except that 150 ml of the solution in the step A of Example 14 was used, a mixture of 100 ml of toluene, 100 ml of chlorobenzene and 17 ml of diethyldiethoxysilane was used in the step B, and 40 ml of THF was used along with 4 ml of isopropanol in the step C, and in the step D, the solid products (II) and (III) were, respectively, treated at 105° C. wherein for the third treatment with TiCl 4 , 200 ml of TiCl 4 was used as the solvent and was maintained at 105° C. for 1 hour, thereby obtaining 9.1 g of solid product (IV).
  • the average particle size of the solid product (IV) was 40.5 ⁇ with particles having a size not larger than 5 ⁇ being contained in an amount of 0.2%.
  • Example 14 The general procedure of Example 14 was repeated except that 114 ml of the solution in the step A of Example 14 was used, 22 ml of methyltriethoxysilane was used as the silane compound in the step B, and a mixture of 50 ml of THF and 2.5 ml of isobutanol was added in the step C, thereby obtaining 8.5 g of solid product (IV) having an average particle size of 43.1 ⁇ .
  • the content of particles having a size not larger than 5 ⁇ was 0.5%.
  • Example 15 The general procedure of Example 15 was repeated except that a mixture of 14 ml of dimethyldiethoxysilane and 2 ml of allyltolmethoxysilane was used as the silane compound in the step B, that 6 ml of t-butanol was used along with 40 ml of THF in the step C, that the temperature prior to heating during the course of from the step B to the step C was kept at a temperature -5° to 0° C.
  • the resultant solid product (IV) had an average particle size of 44.7 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 0.4%.
  • Example 14 The general procedure of Example 14 was repeated except that 170 ml of the solution in the step A of Example 14 was used and 240 ml of toluene, 60 ml of iso-paraffin (Isoper G) and 24 ml of TiCl 4 were used, that 10 ml of cyclohexanol was used along with 27 ml of THF in the step C, and that the treatment with TiCl 4 in the step D was in two stages with the third washing with TiCl 4 being not carried out.
  • the resultant solid product (IV) was obtained in an amount of 11.8 g. It had an average particle size of 37.2 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 0.5%.
  • Example 14 The general procedure of Example 14 was repeated except that 286 g of magnesium propoxide was used in the step A in place of magnesium ethoxide, to which 457 ml of 2-ethyl-1-hexanol and 1550 ml of toluene were added and the mixture was kept at 40° C. for 8 hours while agitating at 500 r.p.m. in an atmosphere of carbon dioxide at 1 kg/cm 2 G to make a uniform solution, after which the carbon dioxide gas was purged and the uniform solution was used as an Mg solution and that in the step C, 12 ml of 2-ethyl-1-hexanol was used instead of ethanol, thereby obtaining 7.8 g of solid product (IV).
  • the resultant solid product (IV) had an average particle size of 44.3 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 0.2%.
  • the slurry after the reaction was transferred under nitrogen sealing conditions to a 5 liter filter equipped with an agitator, a condenser, a thermometer and a nitrogen sealing line and having a heating jacket and a filter unit at the bottom thereof, and subjected to filtration, followed by washing twice with 500 ml of toluene.
  • the analysis of the solid product (IV) revealed 18.0% of Mg, 2.3% of Ti, 57.5% of Cl and 10.7% of di-n-butyl phthalate.
  • the average particle size of the solid product (IV) was 43.6 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 0.2%.
  • Example 14 The general procedure of Example 14 was repeated except that in the step C, ethanol was not used, thereby obtaining 14.3 g of solid product (IV).
  • the average size of the solid product (IV) was 18.5 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 2.3%.
  • Example 14 The general procedure of Example 14 was repeated except that any silane compound was not used in the step B of Example 14 and any alcohol was used in the step C, thereby obtaining 13.8 g of solid product (IV).
  • the average size of the solid product was 6.7 ⁇ and the content of the particles having 5 ⁇ was 41.2%.
  • Example 14 The general procedure of Example 14 was repeated except that 15 ml of TiCl 4 and 5 ml of SiCl 4 were used as a precipitating agent in the step B of Example 14 and a mixed alcohol of 2 ml of isopropanol and 2 ml of ethanol was used, thereby obtaining 10.6 g of solid product (IV).
  • the solid product had an average particle size of 37.5 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 0.6%.
  • Example 14 The general procedure of Example 14 was repeated except that 60 ml of tetrahydropyran was used instead of 50 ml of THF in the step C of Example 14, thereby obtaining 10.0 g of solid product (IV).
  • the solid product (IV) had an average particle size of 33.7 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 0.9%.
  • Example 14 The general procedure of Example 14 was repeated except that 20 ml of n-butanol was used in the step C of Example 14 and 60 ml of 2-methyltetrahydrofuran was used instead of 50 ml of THF, thereby obtaining 12.5 g of solid product (IV).
  • the solid product (IV) had an average particle size of 31.8 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 1.4%.
  • Example 22 The general procedure of Example 22 was repeated except that there was not used the alcohol in the step C of Example 22, thereby obtaining 15.2 g of solid product (IV).
  • the solid product (IV) had an average particle size of 12.5 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 28.3%.
  • Example 23 The general procedure of Example 23 was repeated except that there was not used the alcohol in the step B of Example 23, thereby obtaining 16.7 g of solid product (IV).
  • the solid product (IV) had an average particle size of 14.9 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 17.1%.
  • the catalysts (solid products (IV)) obtained in Examples 21 to 23 and Comparative Examples 8 to 9 were used for carrying out hexane slurry polymerization of propylene.
  • the catalyst obtained in Example 15 was used to carry out bulk polymerization.
  • the yield of the polymer was 210 g with a T-MFR value of 1.8, and the content of ethylene in the polymer was 11.6%.
  • the present invention is more particularly described by way of examples.
  • the mixture was heated at 90° C. for 3 hours in an atmosphere of carbon dioxide at 3 kg/cm 2 G while agitating at 500 r.p.m.
  • the resultant solution was cooled and, after purging of the carbon dioxide gas, was handled under an atmospheric pressure.
  • the solution contained 0.1 g/ml of magnesium ethoxide.
  • the size distribution of the polymer powder is shown in Table 8.
  • Example 27 The general procedure of Example 27 was repeated except that the solution in the step A of Example 27 was used in an amount of 150 ml, the hydrocarbon solvent used in the step B was a mixture of 100 ml of toluene and 100 ml of chlorobenzene, 3 ml of ethanol was used along with 40 ml of THF in the step C instead of the isopropanol, and in the step D, the solid products (II) and (III) were, respectively, treated at 105° C. wherein for the third treatment with TiCl 4 , TiCl 4 was used as the solvent and was maintained at 105° C. for 1 hour, thereby obtaining 9.3 g of solid product (IV).
  • the average particle size of the solid product (IV) was 40.2 ⁇ with particles having a size not larger than 5 ⁇ being contained in an amount of 0.2%.
  • Example 27 The general procedure of Example 27 was repeated except that 114 ml of the solution in the step A of Example 27 was used, 24 ml of tributoxy borane was used in the step B, and a mixture of 50 ml of THF and 4 ml of isobutanol was added in the step C in 1 hour, thereby obtaining 8.2 g of solid product (IV) having an average particle size of 42.3 ⁇ .
  • the content of particles having a size not larger than 5 ⁇ was 0.5%.
  • Example 28 The general procedure of Example 28 was repeated except that 7 ml of cyclohexanol was used in the step C of Example 28 along with 40 ml of THF, the temperature prior to heating during the course of from the step B to the step C was kept at a temperature -5° to 0° C., the temperature rise in the step C was gradual at 1° C./minute, and for the dilution of TiCl 4 in the step D, 100 ml of 1,2-dichloroethane was used instead of 200 to 250 ml of toluene and 2.1 ml of di-n-butyl phthalate was used instead of diisobutyl phthalate.
  • the resultant solid product (IV) had an average particle size of 38.4 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 0.3%.
  • Example 27 The general procedure of Example 27 was repeated except that 170 ml of the solution in the step A of Example 27 was used, 140 ml of toluene, 60 ml of iso-paraffin (Isober G) and 24 ml of TiCl 4 were used, 10 ml of isopropanol was used along with 27 ml of THF in the step C, and the treatment with TiCl 4 in the step D was in two stages with the third washing with TiCl 4 being not carried out.
  • the resultant solid product (IV) had an average particle size of 35.1 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 0.8%.
  • Example 27 The general procedure of Example 27 was repeated except that 286 g of magnesium propoxide was used in the step A in place of magnesium ethoxide, to which 457 ml of 2-ethyl-1-hexanol and 1550 ml of toluene were added and the mixture was kept at 40° C. for 8 hours while agitating at 500 r.p.m. in an atmosphere of carbon dioxide at 1 kg/cm 2 G to make a uniform solution, after which the carbon dioxide gas was purged and the uniform solution was used as an Mg solution and that in the step C, 12 ml of 2-ethyl-1-hexanol was used instead of isopropanol.
  • the resultant solid product had an average particle size of 40.7 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 0.4%.
  • the slurry after the reaction was transferred under nitrogen sealing conditions to a 5 liter filter equipped with an agitator, a condenser, a thermometer and a nitrogen sealing line and having a heating jacket and a filter unit at the bottom thereof, and subjected to filtration, followed by washing twice with 500 ml of toluene.
  • 500 ml of TiCl 4 and 500 ml of toluene were added to the solid product (II) in the filter and maintained at 135° C. for 1 hour at 180 r.p.m.
  • the analysis of the solid product (IV) revealed 18.5% of Mg, 2.35 of Ti, 56.6% of Cl and 7.1% of di-n-butyl phthalate.
  • the average particle size of the solid product (IV) was 45.2 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 0.2%.
  • Example 27 The general procedure of Example 27 was repeated except that in the step C, isopropanol was not used, thereby obtaining 16.9 g of solid product (IV).
  • the average size of the solid product (IV) was 32.8 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 2.1%.
  • Example 27 The general procedure of Example 27 was repeated except that 20 ml of tetraethoxysialne was used instead of the boron compound in the step B, thereby obtaining 16.8 g of solid product (IV).
  • the average size of the solid product was 22.4 ⁇ and the content of the particles having 5 ⁇ was 5.6%.
  • Example 27 The general procedure of Example 27 was repeated except that 15 ml of TiCl 4 and 5 ml of SiCl 4 were used as a precipitating agent in the step B of Example 28 and a mixed alcohol of 2 ml of isopropanol and 2 ml of ethanol was used, thereby obtaining 7.3 g of solid product (IV).
  • the solid product had an average particle size of 36.5 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 0.7%.
  • Example 27 The general procedure of Example 27 was repeated except that 60 ml of tetrahydropyran was used instead of 50 ml of THF in the step C of Example 27, thereby obtaining 9.3 g of solid product (IV).
  • the solid product had an average particle size of 35.8 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 0.8%.
  • Example 27 The general procedure of Example 27 was repeated except that 24 ml of isobutyl borate was used instead of 20 ml of n-butyl borate and 60 ml of 2-methyltetrahydrofuran was used instead of 50 ml of THF in the step C of Example 27, thereby obtaining 8.5 g of solid product (IV).
  • the solid product had an average particle size of 36.1 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 0.7%.
  • Example 35 The general procedure of Example 35 was repeated except that there was not used the alcohol in the step C of Example 35, thereby obtaining 17.3 g of solid product (IV).
  • the solid product had an average particle size of 25.1 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 7.2%.
  • Example 36 The general procedure of Example 36 was repeated except that there was not used the alcohol in the step C of Example 35, thereby obtaining 16.7 g of solid product (IV).
  • the solid product had an average particle size of 27.1 ⁇ and the content of the particles having a size not larger than 5 ⁇ was 6.2%.
  • the catalysts (solid products (IV)) obtained in Examples 34 to 36 and Comparative Examples 12 to 13 were used for carrying out hexane slurry polymerization of propylene.
  • the catalyst obtained in Example 27 was used to carry out bulk polymerization.
  • the yield of the polymer was 192 g with a T-MFR value of 1.4, and the content of ethylene in the polymer was 10.3%.
  • the yield of the polymer was 217 g and the content of the ethylene in the polymer was 50%.
  • Step A Formation of a Magnesium Carbonate Solution
  • the mixture was heated at 90° C. for 3 hours while agitating at 500 r.p.m. in the presence of carbon dioxide.
  • the resultant solution was cooled and the carbon dioxide gas was purged, followed by handling substantially at an atmospheric pressure.
  • the solution contained 0.1 g/ml of magnesium ethoxide.
  • Step D To the solid (II) obtained in Step D were added 200 ml of toluene and 100 ml of TiCl 4 . While agitating at 600 r.p.m., the mixture was heated to 135° C. within 20 minutes, at which it was kept for 1 hour. The agitation was stopped to cause solid (III) to be precipitated, followed by removal of a supernatant liquid by decantation.
  • solid product (IV) had an average size of 37.2 ⁇ with a fine powder having a size not larger than 5 ⁇ being contained in an amount of 0.2%.
  • the results of analysis revealed that the product had 17.3% of magnesium, 2.3% of titanium, 55.6% of chlorine and 8.6% of di-n-butyl phthalate.
  • Example 40 The general procedure of Example 40 was repeated except that 150 ml of the solution obtained in Step A of Example 40 was used, 100 ml of toluene, 100 ml of chlorobenzene and 32 ml of hexamethylcyclotrisiloxane were used in Step B, 40 ml of THF was used in Step C, and for the third treatment with TiCl 4 in Step D, 200 ml of TiCl 4 was used as the solvent and the mixture was kept at 125° C. for 1 hour, thereby obtaining 12.7 g of solid product (IV).
  • the solid product had an average size of 30.5 ⁇ and the content of particles with a size not larger than 5 ⁇ was 0.7%.
  • Example 40 The general procedure of Example 40 was repeated except that a 1 liter autoclave was used for the reactions of Step B and the subsequent steps, 170 ml of the solution obtained in Step A of Example 1 was used in Step B along with 200 ml of toluene, 28 ml of hexamethyl-1,5-diethoxytrisiloxane, 70 ml of THF was used in Step C and the procedure ranging from Step B to Step C was effected under agitation at 400 r.p.m.
  • Example 40 The general procedure of Example 40 was repeated except that 150 ml of the solution obtained in Step A of Example 40 was used, 150 ml of toluene, 50 ml of chlorobenzene and 36 ml of octaethoxy-1,5-dimethyltetrasiloxane were used in Step B, and 60 ml of THF was used in Step C, thereby obtaining solid product (IV).
  • This product had an average size of 25.3 ⁇ and the content of particles with a size not larger than 5 ⁇ was 0.2%.
  • Example 40 The general procedure of Example 40 was repeated except that 114 ml of the solution obtained in Step A was used in Step B of Example 40 along with 140 ml of toluene, 60 ml of iso-paraffin (Isober G), 14 ml of TiCl 4 and 22 ml of hexamethyldisiloxane, 27 ml of THF was used in Step C, and the treatment with TiCl 4 was effected by two stages in Step D where the third washing with TiCl 4 was not performed, thereby obtaining 10.6 g of solid product (IV).
  • the solid product (IV) had an average size of 22.8 ⁇ and the content of particles having a size of not larger than 5 ⁇ was 0.5%.
  • Example 40 The general procedure of Example 40 was repeated except that 286 g of magnesium propoxide was used instead of magnesium ethoxide and 283 ml of 2-ethyl-1-hexanol was used in Step A, thereby obtaining 12.2 g of solid product (IV).
  • the solid product (IV) had an average size of 27.5 ⁇ and the content of particles having a size of not larger than 5 ⁇ was 1.2%.
  • the slurry obtained after the reaction was transferred, under nitrogen-sealing conditions, into a five liter filter equipped with an agitator, a condenser, a thermometer, a sealing line for nitrogen and a heating jacket and having a filter unit, followed by filtration and washing twice with 500 ml of toluene.
  • Example 40 The general procedure of Example 40 was repeated except that any alcohol was not used in Step B of Example 40, thereby obtaining 11.7 g of solid product (IV). In this case, a long time was required for precipitation after which decantation had to be effected over Steps C to D, resulting in a loss of part of fine particles.
  • the content of fine particles with a size of not larger than 5 ⁇ in the resultant solid product (IV) was as high as 4.5%.
  • Example 40 The general procedure of Example 40 was repeated except that any alcohol and any siloxane compound were not used in Step B of Example 40, thereby obtaining 12.3 g of solid product (IV).
  • the content of particles having a size of not larger than 5 ⁇ in the solid product (IV) was 39.2%.
  • Example 43 The general procedure of Example 43 was repeated except that in Step B of Example 43, 20 ml of trimethylchlorosilane was used instead of the siloxane compound.
  • Example 40 The general procedure of Example 40 was repeated except that in Step B of Example 40, 10 ml of dimethyldiethoxysilane was used along with 20 m of hexamethyldisiloxane, thereby obtaining 12.9 g of solid product (IV).
  • the solid product (IV) had an average size of 35.2 ⁇ and the content of particles having a size of not larger than 5 ⁇ was 2.0%.
  • Example 40 The general procedure of Example 40 was repeated except that in Step C of Example 40, 60 ml of tetrahydropyran was used instead of 50 ml of THF, thereby obtaining 10.9 g of solid product (IV).
  • the solid product (IV) had an average size of 21.9 ⁇ and the content of particles having a size of not larger than 5 ⁇ was 6.3%.
  • Example 40 The general procedure of Example 40 was repeated except that in Step C of Examples 40, 32 ml of dimethylpolysiloxane having a viscosity of 10 cps was used instead of 25 ml of hexamethyldisiloxane and 60 ml of 2-methyltetrahydrofuran was used instead of 50 ml of THF, thereby obtaining 13.1 g of solid product (IV).
  • the solid product (IV) had an average size of 29.8 ⁇ and the content of particles having a size of not larger than 5 ⁇ was 2.7%.
  • Example 48 The general procedure of Example 48 was repeated except that hexamethyldisiloxane and any alcohol were not used in Step B of Example 48, thereby obtaining 10.5 g of solid product (IV).
  • the solid product (IV) contained a large quantity of fine particles and the content of fine particles with a size of not larger than 5 ⁇ was 29.7%.
  • Example 49 The general procedure of Example 49 was repeated except that any siloxane compound was not used in Step B of Example 49, thereby obtaining 13.6 g of solid product (IV).
  • the solid product (IV) contained a large quantity of fine particles and the content of fine particles with a size of not larger than 5 ⁇ was 11.3%.
  • the catalysts (solid products (IV)) obtained in Examples 47 to 49 and Comparative Examples 17 and 18 were used to carry out the hexane slurry polymerization of propylene.
  • Example 41 The catalyst obtained in Example 41 was used for bulk polymerization.
  • the yield of the polymer was 169 g and the ethylene content in the polymer was 48%.

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US5227354A (en) * 1991-07-17 1993-07-13 Amoco Corporation Olefin polymerization and copolymerization catalyst
US5332707A (en) * 1992-07-31 1994-07-26 Amoco Corporation Olefin polymerization and copolymerization catalyst
US6538079B2 (en) * 2000-03-30 2003-03-25 Sumitomo Chemical Company, Limited Process for producing catalyst for ethylene polymerization and process for producing ethylene polymer

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US5556820A (en) * 1989-12-28 1996-09-17 Idemitsu Petrochemical Co., Ltd. Catalyst component for olefin polymerization and process for producing polyolefins
EP0544006B1 (de) * 1991-06-17 1996-11-06 Idemitsu Petrochemical Co. Ltd. Herstellung eines bestandteils eines katalysators für die olefinpolymerisation
WO1994015977A1 (en) * 1992-12-31 1994-07-21 Shell Polypropylene Company Olefin polymerization catalyst
ATE183522T1 (de) * 1993-02-16 1999-09-15 Huels Chemische Werke Ag Olefinpolymerisationskatalysator
US20030022786A1 (en) 2001-05-03 2003-01-30 Epstein Ronald A. Catalyst for propylene polymerization
KR100431457B1 (ko) * 2001-06-18 2004-05-12 주식회사 엘지화학 올레핀 중합용 고활성 촉매의 제조방법, 및 이를 이용하는폴리올레핀의 제조방법
EP1454921B1 (de) * 2001-09-21 2021-07-28 Tokuyama Corporation Radikalpolymerisationskatalysatoren und klebekit für die zahnärztliche verwendung

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